Synthesis and molecular structures of neutral nickel complexes. Catalytic activity of (Benzamidinato)(acetylacetonato)nickel for the addition polymerization of norbornene, the oligomerization of ethylene, and the dimerization of propylene

Elza Nelkenbaum; Moshe Kapon; Moris S. Eisen

doi:10.1021/om0490379

Synthesis and molecular structures of neutral nickel complexes. Catalytic activity of (Benzamidinato)(acetylacetonato)nickel for the addition polymerization of norbornene, the oligomerization of ethylene, and the dimerization of propylene

Elza Nelkenbaum, Moshe Kapon, Moris S. Eisen^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

74 Scopus citations

Abstract

The new neutral nickel complexes PhC(NSiMe₃)₂Ni(acac) (3), PhC(NSiMe₃)₂Ni(acac)-(TMEDA) (4), [PhC(NSiMe ₃)₂]₂Ni₂ (5), [PhC(NSiMe ₃)₂]₂Ni·Li₂Br ₂(TMEDA)₂ (6), (TMEDA)₂Ni (7), p-MePhC(NSiMe₃)₂Ni(acac) (8), p-MePhC(NSiMe ₃)₂Ni(acac)(TMEDA) (9), [p-MePhC-(NSiMe₃) ₂]₂Ni (10), NiMe₂Py₂ (11) and [p-MePhC(NSiMe₃)]₂Ni(Py) (14) have been synthesized and characterized. The solid-state molecular structures of all complexes have been confirmed by low-temperature X-ray diffraction analysis. The methyl complex p-MePhC(NSiMe₃)₂Ni(Me)(Py) (13) is not stable and rapidly decomposes, forming the complex [p-MePhC(NSiMe₃)]₂-Ni(Py) (14). Complex 3 activated with MAO has been shown to be an efficient catalytic system for the norbornene vinyl-type polymerization. The activity of the catalyst and the molecular weights of the resulting polynorbornenes were found to be dependent on the reaction time, the MAO/precatalyst ratio, and the reaction temperature. In addition, this catalytic system has been found to dimerize propylene to a mixture of hexenes with a high turnover frequency of η = 9040 h^-1 and oligomerize ethylene to either a mixture of C₄-C₆ or/and C₄-C₁₄ products, depending on the temperature and the solvent, extremely rapidly (η = 83 500 h^-1).

Original language	English
Pages (from-to)	2645-2659
Number of pages	15
Journal	Organometallics
Volume	24
Issue number	11
DOIs	https://doi.org/10.1021/om0490379
State	Published - 23 May 2005
Externally published	Yes

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@article{67d9d714e3f64107bcd091bd038c2762,

title = "Synthesis and molecular structures of neutral nickel complexes. Catalytic activity of (Benzamidinato)(acetylacetonato)nickel for the addition polymerization of norbornene, the oligomerization of ethylene, and the dimerization of propylene",

abstract = "The new neutral nickel complexes PhC(NSiMe3)2Ni(acac) (3), PhC(NSiMe3)2Ni(acac)-(TMEDA) (4), [PhC(NSiMe 3)2]2Ni2 (5), [PhC(NSiMe 3)2]2Ni·Li2Br 2(TMEDA)2 (6), (TMEDA)2Ni (7), p-MePhC(NSiMe3)2Ni(acac) (8), p-MePhC(NSiMe 3)2Ni(acac)(TMEDA) (9), [p-MePhC-(NSiMe3) 2]2Ni (10), NiMe2Py2 (11) and [p-MePhC(NSiMe3)]2Ni(Py) (14) have been synthesized and characterized. The solid-state molecular structures of all complexes have been confirmed by low-temperature X-ray diffraction analysis. The methyl complex p-MePhC(NSiMe3)2Ni(Me)(Py) (13) is not stable and rapidly decomposes, forming the complex [p-MePhC(NSiMe3)]2-Ni(Py) (14). Complex 3 activated with MAO has been shown to be an efficient catalytic system for the norbornene vinyl-type polymerization. The activity of the catalyst and the molecular weights of the resulting polynorbornenes were found to be dependent on the reaction time, the MAO/precatalyst ratio, and the reaction temperature. In addition, this catalytic system has been found to dimerize propylene to a mixture of hexenes with a high turnover frequency of η = 9040 h-1 and oligomerize ethylene to either a mixture of C4-C6 or/and C4-C14 products, depending on the temperature and the solvent, extremely rapidly (η = 83 500 h-1).",

author = "Elza Nelkenbaum and Moshe Kapon and Eisen, {Moris S.}",

year = "2005",

month = may,

day = "23",

doi = "10.1021/om0490379",

language = "英语",

volume = "24",

pages = "2645--2659",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "11",

}

Synthesis and molecular structures of neutral nickel complexes. Catalytic activity of (Benzamidinato)(acetylacetonato)nickel for the addition polymerization of norbornene, the oligomerization of ethylene, and the dimerization of propylene. / Nelkenbaum, Elza; Kapon, Moshe; Eisen, Moris S.
In: Organometallics, Vol. 24, No. 11, 23.05.2005, p. 2645-2659.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Synthesis and molecular structures of neutral nickel complexes. Catalytic activity of (Benzamidinato)(acetylacetonato)nickel for the addition polymerization of norbornene, the oligomerization of ethylene, and the dimerization of propylene

AU - Nelkenbaum, Elza

AU - Kapon, Moshe

AU - Eisen, Moris S.

PY - 2005/5/23

Y1 - 2005/5/23

N2 - The new neutral nickel complexes PhC(NSiMe3)2Ni(acac) (3), PhC(NSiMe3)2Ni(acac)-(TMEDA) (4), [PhC(NSiMe 3)2]2Ni2 (5), [PhC(NSiMe 3)2]2Ni·Li2Br 2(TMEDA)2 (6), (TMEDA)2Ni (7), p-MePhC(NSiMe3)2Ni(acac) (8), p-MePhC(NSiMe 3)2Ni(acac)(TMEDA) (9), [p-MePhC-(NSiMe3) 2]2Ni (10), NiMe2Py2 (11) and [p-MePhC(NSiMe3)]2Ni(Py) (14) have been synthesized and characterized. The solid-state molecular structures of all complexes have been confirmed by low-temperature X-ray diffraction analysis. The methyl complex p-MePhC(NSiMe3)2Ni(Me)(Py) (13) is not stable and rapidly decomposes, forming the complex [p-MePhC(NSiMe3)]2-Ni(Py) (14). Complex 3 activated with MAO has been shown to be an efficient catalytic system for the norbornene vinyl-type polymerization. The activity of the catalyst and the molecular weights of the resulting polynorbornenes were found to be dependent on the reaction time, the MAO/precatalyst ratio, and the reaction temperature. In addition, this catalytic system has been found to dimerize propylene to a mixture of hexenes with a high turnover frequency of η = 9040 h-1 and oligomerize ethylene to either a mixture of C4-C6 or/and C4-C14 products, depending on the temperature and the solvent, extremely rapidly (η = 83 500 h-1).

AB - The new neutral nickel complexes PhC(NSiMe3)2Ni(acac) (3), PhC(NSiMe3)2Ni(acac)-(TMEDA) (4), [PhC(NSiMe 3)2]2Ni2 (5), [PhC(NSiMe 3)2]2Ni·Li2Br 2(TMEDA)2 (6), (TMEDA)2Ni (7), p-MePhC(NSiMe3)2Ni(acac) (8), p-MePhC(NSiMe 3)2Ni(acac)(TMEDA) (9), [p-MePhC-(NSiMe3) 2]2Ni (10), NiMe2Py2 (11) and [p-MePhC(NSiMe3)]2Ni(Py) (14) have been synthesized and characterized. The solid-state molecular structures of all complexes have been confirmed by low-temperature X-ray diffraction analysis. The methyl complex p-MePhC(NSiMe3)2Ni(Me)(Py) (13) is not stable and rapidly decomposes, forming the complex [p-MePhC(NSiMe3)]2-Ni(Py) (14). Complex 3 activated with MAO has been shown to be an efficient catalytic system for the norbornene vinyl-type polymerization. The activity of the catalyst and the molecular weights of the resulting polynorbornenes were found to be dependent on the reaction time, the MAO/precatalyst ratio, and the reaction temperature. In addition, this catalytic system has been found to dimerize propylene to a mixture of hexenes with a high turnover frequency of η = 9040 h-1 and oligomerize ethylene to either a mixture of C4-C6 or/and C4-C14 products, depending on the temperature and the solvent, extremely rapidly (η = 83 500 h-1).

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U2 - 10.1021/om0490379

DO - 10.1021/om0490379

M3 - 文章

AN - SCOPUS:20444506476

SN - 0276-7333

VL - 24

SP - 2645

EP - 2659

JO - Organometallics

JF - Organometallics

IS - 11

ER -

Synthesis and molecular structures of neutral nickel complexes. Catalytic activity of (Benzamidinato)(acetylacetonato)nickel for the addition polymerization of norbornene, the oligomerization of ethylene, and the dimerization of propylene

Abstract

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